New colouring process



2,944,871 Patented July 12., 1960 NEW COLUURHJG PROCESS John Reginald Atkinson, Gerald Booth, Eric Leslie Johnson, and Walter Percival Mills, Manchester, England, assignors to Imperial Chemical Industries Limited, London, England, a corporation of Great Britain No Drawing. Filed Sept. 24, 1953, Ser. No. 762,923

Claims riority, application Great Britain Oct. 4, 1957 '11 Claims. (Cl. 8-41) This invention relates to a new colouring process and more particularly it relates to a new process for the production of fast colourations on textile materials made from synthetic polymers.

Ithas been found that water-insoluble azo dyestuffs containing alkyl groups substituted by epoxy, chloro or bromo groups when applied from aqueous dispersion to textile materials made from synthetic polymers, for example polyamides and basically modified .polyacrylonitriles, give colourations of unexpectedly high fastness to wet treatments. Colourations effected on these textile materials by the use of water-insoluble azo dyestuffs not containing these. groups are in general deficient in fastness to wet treatments, and the colourations obtained by the use, of water-insoluble azo'dyestuffs containing these groups are markedly superior in fastness to wet treatmehts not only in that they retain their strength of shade better but also in that staining ofadjacent textile materials is much reduced. It seems probable that this fastn'ess is due at least in part to chemical reaction of the dyestuli with the textile material.

According to the invention there is provided a process for the colouration of synthetic polymeric textile materials which comprises treating a synthetic polymeric textile material with a water-insoluble azo dyestufi containing at least one alkoxy or alkylamino radical which is substituted by an epoxy group or a chlorine or bromine atom.

As examples of the alkoxy or alkylamino radicals sub- 'st'ituted by an epoxy group or a chlorine or bromine atom there may be mentioned B-chloroethoxy, fl-bromoethoxy, B-chloropropoxy, fi-bromopropoxy, 'y-chloro-B- hyd'roxypropoxy, 'y-bromo=B-hydroxypropoxy, fly epoxypro er-y, B-chloroethylamino, B-bromoethylamino, fibromopropylamino, B-chloropropylamino, "y-ChlOIO-fi-hY- droxypropylamino, -brmo-B-h-ydroxypropylamino, fil r epoxypropylamino, N:N-di(fi-chloroethyl)amino, NzN- (iii 13 -'brorno ethyl)amino, NrN di('y chloro-fi-hydroxypropyl) amino, N:N-di('y-bromo-B-hydroxypropyl) amino, N:N -di-(B:' epoxypropyl)amino, N-B-chloroethyl-N-B- methoxyethylamino, N-B-brom'oethyl-N-ethylamino, N-ybromo ,6} hydr'oxypropyl N-B-cyanoethylamino, N-flrfepoxypropyl i N-methylamino, N- -chloro-fi-hydroxypropyl-N-fl ethoxyethylamino and N- -chloro-B-hydroxypropyl-N-B hydroxyethylamino. The water-insoluble azo dyestutf as hereinbefore defined, or mixtures thereof may be applied to a synthetic polymeric textile material by a dyeing or printing process and it is preferred to use the water-insoluble azo dyestulf in the form of an aqueous dispersion or a re-dispersibl'e powder. The aqueous dispersion of the waterinsoluble azo dyestulf may be obtained by gravel-milling the dyestuif in water in the presence of a dispersing agent, for example the sodium salt of sulphonated naphthalene formaldehyde condensation products, sulphosuccinic acid esters, Turkey red oil and condensation products of alkyl phenols with ethylene oxide, and if desired in the presence of a protective colloid, for example' dextrin. If

desired the aqueous dispersion so obtained may be converted to a re-dispersible powder by any of the processes known for forming re-dispersible powders.

The application of the water-insoluble azo dyestufi as hereinbeforedefined to the synthetic polymeric textile material by a dyeing process may be carried out by immersing the synthetic polymeric textile material in a dyebath containing an aqueous dispersion of the waterinsoluble azo dyestuif and heating at a temperature at or near the boiling point of the dyebath, for example at a temperature between and C. If desired the dyebath can be heated at temperatures above 100 C., for example. at a temperature between 100 and 130 C. under super-atmospheric pressure. The dyed textile material is thenremoved from the dyebath, rinsed in water, and dried. j

The water-insoluble azo dyestuffs, as hereinbefore defined, may also be applied to the synthetic polymeric textile material by a printing process which may be efiected by printing the synthetic polymeric textile material with a, thickened printing paste containing an aqueous dispersion of the water-insoluble azo dyestuif. The printing pastemay be thickened with any of the usual thickening agents, for example methyl cellulose, starch, locust bean gum, N'afka crystal gum, or sodium alginate, and may contain normal adjuvants for printing pastes such as urea, thiourea or thiodiglycol or adjuvants used for the application of water-insoluble dyes such as methylated spirits, sodium meta=nitrobenzenesulphonate or aqueous emulsions of sulphonated oils.

The printing paste may be conventiently applied to the synthetic polymeric textile material by printing with block,spray, stencil, screen or roller, preferably drying the printed material, and if desired steaming at atmospheri'c pressure or in a closed vessel at super-atmospheric pressure when a temperature above 100 (3., preferably between and (3., is required.

When the synthetic polymeric textile material is coloured with a water-insoluble azo dyestutf as hereinbefore defined, which also contains a primary amino group then, if desired, the dyed textile material may be treated with an aqueous solution of nitrous acid and a coupling component, whereby another azo 'dyestuif is formed in situ on the textile material.

As examples of synthetic polymeric textile materials which may be used in the process of the invention there may be mentioned textile materials, comprising polyamides, for example polyhexamethylene adipamide and thepolyrnerfrom caprolactam and modified polyacrylonitriles.

" The water-insoluble azo dyestuffs, as hereinbefore defined, which aroused in the process of the invention may be obtained by diazotising a primary aromatic amine I andcoupling the diazo compound so obtained with a coupling componentf'the primary aromatic amine and coupling coifipo'nent' being so chosen that the resultant azo 'dyestuii is free from sulphonic acid and carboxylic acid groups and contains at least one alkoxy or alkylanfino' radicals substituted by an epoxy group or a chlorineor bromine-atom.

Asex-amples of primary aromatic arnines'which may be-used to obtain theWater-ins'oluble azo dyestufis there may be mentioned p-nitroaniline, oand p-aminobenzo- -nitrile, 4-arninb-3-chlorobenzonitnile, Z-amino-S cyanobenzotrifiuoriii 'e, 2 :4-dicyanoaniline, oand p-aminophenyl methyl sulphone, 4-amino-3-chlorophenyl ethyl sulphone, 4-a'mino-3 -chlorophenyl B-hydroxyethyl sulphone, 2E441i(methylsulphonyllaniline, 2:5-di(ethylsulphonyl) aniline, 3:4-di(ethyl'sulphonyl) aniline, Zamim- 5-r'r-iethylsulphonylbenzotriliuoride, p 1 aminobenzenesul phonamide, 4-amino-3 -chlorobenzenesulphonamide 4 -ehlorobenzenesulphon-fl hydroXyethyla-mifle, 2-

amino-6-methylsulphonylbenzthiazole, 2-amino-6 nitrobenzthiazole, 2 amino nitrothiazole, p (,6 chloroethoxy) aniline, p ('y chloro-B-hydroxypropoxy) aniline, p-('y-bromo-fi-hydroxypropoxy) aniline, p,- ('y-bromopropoxy) aniline and p-(fiz'y-epoxypropoxy) aniline.

As examples of coupling components there may be mentioned 1-N:N-di(B-chloroethyl)amino-3-methy1benz ene, 1 NzN-di(p-bromoethyl) amino-3-methylbenzene, N-ethyl-N-y-chloro-p-hydroxypropylaniline, N-ethyl N- fl-y-epoxypropylaniline, N:N L di(' -chloro-fl-hydroxypropyl) aniline, N N-di(fl: epoxypropyl) aniline, l-N :N-diy-chloro-fl-hydroxypropyl)-amino-2-methoxy 5 methylbenzene, 1 N:N-di(v-chloro-5hydroxypropyl) amino- 3-methylbenzene, l-N:N-di-('y-chloro-B-hydroxypropyl)- amino-3-chlorobenzene, N:N di ('y-bromo-fl-hydroxypropyl) aniline, N ethyl-N-(-y-bromo-fi-hydroxypropyhaniline, 1 N ('y-chloro-p-hydroxypropyl) -3-methylben zene, l-N-('y-chloro-fl-hydroxypropyl) aminonaphthalene, l-N-p-methoxyethyl-N-(y chloro B hydroxypropyl) amino-3-methylbenzene, N-ethyl-N-fl-bromoethylaniline, l-N-ethyl-N (flz'y epoxypropyl)amino 3 methylbenz ene, 1 N-ethyl-N-('y-bromo-fi-hydroxypropyl) amino-3- methylbenzene, N43-hydroxyethyl-N-'y-chloro-p-hydroxypropylaniline, 1 N:N di('y chloro-p-hydroxypropyD- amino-Z-methoxy 5 acetamidobenzene, 1 N:N di("ychloro-B-hydroxypropyl)amino-3 acetamidobenzene, 3- N:Ndi('y-chlor0 ,8 hydroxypropyl) aminobenzotrifluoride, cresidine, dimethylaniline, N-ethyl-N-fi-hydroxyas hereinbefore defined, which may be used in the process of the invention are the water-insoluble monoazo dyestuifs of the formula:

Z CH:.CHOH.CH2X

CH2.CHOH.CH2X

wherein R represents an :alkyl or acylamino group or a hydrogen or a halogen atom, X represents a chlorine or a bromine atom, Y represents a cyano, alkylsulphonyl, aminosulphonyl or substituted aminosulphonyl group which is situated in an ortho or para position to the azo bond, and Z represents a hydrogen or a halogen atom or a trifluoromethyl, cyano, alkylsulphonyl, aminosulphonyl or substituted aminosulphonyl group. 7

As examples of the atoms and groups represented by R there may be mentioned hydrogen, chlorine, bromine, methyl and acetylamino.

As examples of the groups represented by Y there may be mentioned cyano, methylsulphonyl, ethylsulphonyl, t9 hydroxyethylsulphonyl, aminosulphonyl, dimethylaminosulphonyl and fi-hydroxyethylaminosulphonyl and as examples of the atoms and groups represented by Z there may be mentioned, chlorine, bromine, trifluoromethyl, cyano, methylsulphonyl, ethylsulphonyl and aminosulphonyl.

The preferred water-insoluble azo dyestufis of the above formula when applied to synthetic polyamide textile materials by the process of the invention give bright orange to rubine shades which have excellent fastness to light and to washing.

The invention is illustrated but not limited by the following examples in which parts and percentages are by weight.

Example 1 1 part of 4-nitro-4'-N:N-di('y-chloro-[i-hydroxypropyl) amino azobenzene is dispersed in 20 parts of Water by milling in the presence of a sodium salt of a sulphonated naphthalene formaldehyde condensation product and the dispersion so obtained is added to 4,000 parts of water containing 4 parts of a condensate of ethylene oxide with a fatty alcohol. 100 parts of polyamide textile material are placed in the dyebath so obtained and the dyebath is then heated to C. and maintained at that temperature for 60 minutes. The polyamide textile material is then rinsed in water, immersed for 30 minutes in a hot aqueous solution containing 0.2% of sodium carbonate and 0.1% of a condensate of ethylene oxide with an alkyl phenol, again rinsed in water and dried. The polyamide textile material is dyed a red shade of very good fastness to washing.

Example 2 In place of the 1 part of the dyestulf used in Example 1 there is used 1 part of 4-nitro-4-'[N-ethyl-N-(3-chloro- 2-hydroxypropyl) l-aminoazobenzene or 1 part of 4-nitro- 4-(N-ethyl-N-2:3 epoxypropyl) aminoazobenzene when the polyamide textile material is dyed in red shades of very good fastness to washing.

Example 3 1 part of 4-nitro-4-N:N-di('y-chloro-p-hydroxypropyl) amino azobenzene is dispersed in 20 parts of water as I described in Example 1 and the dispersion so obtained is added to 4000 parts of Water containing 1.5 parts of oleyl sodium sulphate at 50 C. parts of the basical ly modified polyacrylonitrile textile material manufactured by the Chemstrand Corporation and sold under their trade mark Acrilan are placed in the dyebath so obtained and the dyebath is then heated to a temperature between'98" C. and 100 C. and maintained at that temperature for 60 minutes. The modified polyacrylonitrile textile material is then rinsed in water, immersed for 30 minutes in a hot aqueous solution containing 0.05% of sodium carbonate and 0.2% of a condensate of ethylene oxide with an alkyl phenol, again rinsed in water, and dried. The modified polyacrylonitrile textile material is dyed a red shade of very good fastness to wet treatments.

Example 4 In place of the 1 part of the dyestufi used in Example .1 there is used 1 part of .4-nitro-4'-N:N-di(fl:'y-epoxy- .propyl) aminoazobenzene, when the polyamide textile material is similarly dyed a red shade possessing similar fastness properties.

shades obtained on polyamide textile material when the water-insoluble azo dyestufis, obtained by diazotising the amine listed in the second column of the table and I coupling with the coupling. component listed in the third column of the table, are applied to polyamide textile materials by the method described in Example 1.

The following table gives further examples of the Q Shad'eon t Bhade age Example Amine OoupllngfComp onent Polyamlde Example Amine Coupling Gomponen o ggtru h a i r iia ls Materials let. 48 2-amlno-5-nitrothial-N-ethyl-N-Bry- Blue.

Z-amino-E-eyano-ben- N .N di(- ehloro B Scar e 0 mp lamina 11 -.----do N-ethyl-N-v-chloro- Red. 49- do l-lgieltrlyg-ggbgggloo.

1 iiiii g amino-3-methyl- V a benzene.

" '4-amlno-3-ehlorodo Scarlet. n" N hydmxyethyl N Reddish- 12- i methyl Sm 60 "do 'y ehlolro-gl-hydroxyblue.

p one. r am me.

Z'ammo'amethyl 51 do l-l lii dlby-chloro-fl- Greenlshsulphonyl bemon hydroxypropyl) blue. mfluoflde. R d amino-2 Ineth0xy-5- 14 ii iiiihiii' nuad'o "I n e I 15 acetamldobenzene.

on a 9'. 15 2-zi niiu fi-nitro-thlado Blue.

e. 16 pmtmnflme i y lfig'fiififiifih- Example 52 17 do N e ti i'yl-N-v-bromo- Do. 20 parts of a 5% aqueous d-1spers1on of 4-n1tro-4 (N- g 20 ethyl-N-pz'y-epoxypropyl)ammoazobenzene are1 mixer;

a f ea 2 parts of an aqueous emu sron o 2- mlno-fi-nitro-thla- N-ethyl-N-y-bromo- Dark blue. w th 10 parts 0 ur I 18 g' g sulphonated sperm 011 and pinef 01l,t1 pacrlt 6%flssrdgugiii h nate arts 0 wa er an r 19. 4-amino-3-ehloro-ben- N-etfiiyilglmgbromo Orange mmtrobenesulp Q a p f N fka c Stal um The Zen-e Sulphmamme' at Scarlet a 30% aqueous solution 0 a ry g 20mm l i d oxr lllillliTlggi-nggoprinting paste so obtained is applied from a roller printgtglysulpfine' methynienzene' Red ing machine to a polyamide textile material. The poly- 21 p-mtmanflme Nillglgllggileiggyamide textile material is dried and then exposed for 15 23 m 2-ggltirnoiiiqgegilylpolyamide textile matenal so obtained s rinsed n col i i Vibe water and soaped at 80 C. in a solution contammg 2 2 ZEIgggHItw-thia- Violetparts of soap in 1000 parts of water. The printed poly- 2016' 3 hl N ethyl Ne epoxy Scarlet amide textile material is then rinsed 1n Water and dried. ro- I 25mm" lizgglglecthglslm PYPY18m1me- A bright reg printdis OIIPtZItHCd WhlCh has excellent fast p ness to was ng an 0 1g ----.do Red. v

26 zigntirlilfloufilgfio ben 1 What we clalm as: I

27mm z'aniim'fi'nitm'tma' 1. Process for the coloration of synthetic polymeric 28 Peres textile materials selected from the class consisting of gil iii polyamide and modified polyacrylomtrile textile materials which comprises treating the send synthetic polybr mo-B-hytiii. Do. meric textile materials w1th a water-insoluble azo dyesommn giT-Mipmmxy) "nstuff containing at least one group selected fl'inilkflile class aniline' f n lalkox w-oxirany a y amino,

' Redconsistm o to cram y y 31 n p-mtmanflme ugigdgg'lcligggl) NzN-dfli-oxiranylalkyl)amino, w-chloroalkoxy, w-hrolfiiiii moalkoxy, w-chloroalkylamino, w-bromoalkylammo,

32 Smlet- N:N-di(w-chloroalkyl)amino, and N:N-d1-(w-bromoalpfienyl ethyl sulkyl amino. I

33 2. Process as claimed in claim 1, wherem said dyestufi ill?" sulphonom g I has an w-chloroalkoxy group which also contains a caram 34 Blue v binol group vicinal to the w-carbon atom. 35 pi o n ne h-chloro-fl- Maroon- 3, Process as claimed in claim 1, wherein said dye- 3fi stufi has an w-bromoalkoxy group WhlCh also contams g-metilyl-benzene' a carbinol group vicinal to the ii-carbon atom.

36 4. Process as claimed in claim 1, wherein said dyeggggg-l ethylsulstuff has an w-ch-loroalkylamino group which also con- 37 35?" tains a carbinol group vicmal to the w-carbon atom.

Zjgfigggiiggga- Bluish' 5. Process as claimed in claim 1, wherem said dye- 38 Z919 11111 N-N di( chloro- Rgr i stufi has an w-bromoalkylamino group which also con- 39 p-mtm e l-hygdrnlxygilpyn I tains a carbinol group vicina'l to the w-carbon atom.

ii ili' 6 Process as claimed in claim 1, wherein said dye- DZ u phenyl ethyl Sulalso contains two carbinol groups each of which is vrcmal 2-8PIDi EE 5-DitTO h B' Violet- ,to an carbon ato 'f I I zole' 1-N- -ehloro-fl-hy- Red. 7. Process as claimed in claim 1, wherein said yep-mtmanume n fg stuif has an N:N-di(w-br0rnoalkyl)amino grfouphwlllnch slmethy emene' carbinol rou s each 0 w 1c is 43 4-amino-3-chlor0- N-vo o-fig i 5 also contains twob atom g p benzene g fi vicmal to an w-car on amide' dii yam e. Rubifle- 8. Process as claimed in claim 1, wherein said Water- 44 fifigglsgltgi insoluble azo dyestufi is applied to the synthetic poly- Sulphone" 1 -t Xtile material by dyeing.

45 2-2mg'JM-mtmtmaligglgggpwggo B ue 9 Pr: cess as claimed in claim 1, wherein said Wateriilgfirilgzmethyb insoluble azo dyestuif is applied to the synthetic polyamin 8th meric textile material by print ng.

46-0..- z-mtmgmalgole'y D 10. Process for the coloration of synthetic polymeric 47 z-animolfilnimtma 'hfififiififiiiiy' on textile materials selected from the class consistingof 20 e. dmxypmpylammo polyamide and modified polyacrylomtnle textile materra s 3-methylbenzene.

which comprises treating the said synthetic polymeric textile materials with a water-insoluble azo dyestufl of the formula:

0H,.0HOH.GH,X

Y CH2.CHOH.CH3X

which is situated with respect to the azo bond in a 15 position selected from ortho and para and Z is selected from the class consisting of hydrogen, halogen, trifiuoromethyhcyano, alkylsulfonyl, aminosulfonyl, and sub stituted aminosulfonyl. v

11. Synthetic polymeric textile materials selected from the class consisting of polyamide and modified polyacrylonitrile. textile materials colored with a waterinsoluble azo dyestuflf containing at least one group selected from the class consisting of w-oxirany-lalkoxy, woxiranylalkylamino," N:N-di(w-oxiranyla1ky1) amino, chloroalkoxy, w-bromoalkoxy, w-chloroalkylamino, whromoalkylamino, N'zN di(w chloroalkybamino, and N :N-di(w-bromoalky1) amino.

No references cited. 

1. PROCESS FOR THE COLORATION OF SYNTHETIC POLYMERIC TEXTILE MATERIALS SELECTED FROM THE CLASS CONSISTING OF POLYAMIDE AND MODIFIED POLYACRYLONITRILE TEXTILE MATERIALS WHICH COMPRISES TREATING THE SAID SYNTHETIC POLYMERIC TEXTILE MATERIALS WITH A WATER-NINSOLUBLE AZO DYESTUFF CONTAINING AT LEAST ONE GROUP SELECTED FROM THE CLASS CONSISTING OF W-OXIRANYLALKOXY, W-OXIRANYLALKYLAMINO, N:N-DI(W-OXIRANYLALKYL) AMINO, W-CHLOROALKOXY, W-BROMOALKOXY, W-CHLOROALKYLAMINO, W-BROMOALKYLAMINO, N:N-DI(W-CHLOROALKYL) AMINO, AND N:N-DI-(W-BROMOALKYL) AMINO. 